Vinyl 2,2-dimethyl-3-marpholinocarbonylcyclobutane acetate

ABSTRACT

The invention provides certain vinyl ester amides of pinic acid, particularly vinyl 2,2-dimethyl-3morpholinocarbonylcyclobutane acetate, which can be prepared by selective amination followed by vinyl interchange, and are copolymerizable with vinyl chloride.

United States Patent Glen W. Hedrick Lake City, Fla.;

Frank C. Magne, New Orleans, La. [2!] Appl. No. 870,850

[22] Filed Aug. 6, 1969 [72] lnventors [23] Division of Ser. No.647,343, June 30, 1967,

Pat. No. 3, 544, 529. V s [45] Patented Sept. 28, 1971 [73] Assignee TheUnited States of America as represented by the Secretary of Agriql ltnre[54] VINYL 2,2-DlMETHYL-3- MARPROLINOCARBONYLCYCLOBUTANE ACETATE 1Claim, No Drawings [52] U.S. Cl 260/2472 B [51] Int. Cl C07d 87/36 [50]Field of Search 260/2472 [56] References Cited OTHER REFERENCES J. H.Griffith et al. Chemical Abstracts, Vol. 65, page 12, 297 (1966) PrimaryExaminerAlex Mazel Assistant Examiner.lose Tovar AttorneysR. Hoffman andW. Bier VINYL 2,2-DlMETHYL-3- MARPHOLINOCARBONYLCYCLOBUTANE ACETATE Thisapplication is a division of Ser. No. 647,343, filed June 30,1967, nowU.S. Pat. No. 3,544,529.

A nonexclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

A primary object of the present invention is to vinyl ester amides ofpinic acid, particularly vinyl 2,2-dimethyl-3-morpholinocarbonylcyclobutane acetate. Other objects of the inventioninclude the provision of methods forpreparingsaid vinyl ester amides andmethods for preparing vinyl chloride o A; ll CH2=CHO- CH,- CY

CH CH;

5 aw Copolymers containing approximately and 30 weight percent of thevinyl ester-amide were prepared to examine the ability of thesecomonomers to act as internal plasticizersfor the polymers.

The vinyl esters of 2,2-dimethyl-3-alkylaminocarbonylcyclobutane aceticacid were prepared by reacting the following amino morpholine,piperidine and di-n-butyl amine with ethyl2,2-dimethyl-3-chlorocarbonylcyclobutane acetate, by hydrolyzing theethyl ester to the free acid and vinylatingthe resulting monoamides byvinyl interchange. Results are shown in table I.

The vinyl chloride copolymers containing approximately and weightpercent of the vinyl ester-amide were prepared in an emulsion system at60 C. using ORR' soap as the emulsifying agent and potassium persulfateas the initiator. The copolymers were reprecipitated 15 times fromtetrahydrofuran into water and three times into methanol beforeanalysis.

The evaluations of the copolymers obtained on'specimens die-cut from37-54 mil thick sheets prepared by casting on a confined mercurysurface, a tetrahydrofuran'solution containing 15 grams of therespective copolymers 0.075 gram of stearic acid and 0.15 gram ofAdvastab T-360 stabilizer (a polymeric tin mercaptide-Advance Division,Carlisle Chemical Works). After setting for 48 hours at room temperatureto allow the bulk of the solvent to evaporate, the sheets were strippedfrom the mercury surface and aged .for 24 hours at room temperature.They were then heated in a forced draft oven for 12 hours at 65 C.followed by another aging at room temperature for 30 days todesolventize the film. The copolymers were then tested for tensilestrength, modulus of elasticity, yield point and elongation measurementswere made in conformance with ASTM Test D638 for rigid and semirigidconditions, except for the use of l-inch gauge length rather than the 2inches called for in the test. Torsional stiffness measurements weremade in conformance to ASTM Test l0436 l T. The results of these testsare shown in table vlll.

EXAMPLE 1 The acid chloride, hp. 1 14C., 2 mm., of monoethyl pinate, wasprepared by reacting thionyl chloride with the monoester obtained byesterification of pinic acid with one mole of ethanol (Lewis, J. B., andHedrick, G. W., J.Org. Chem., 24, 49 1870 (1959)). The pinic acid wasobtained" from hypochlorite oxidation of cis-dl-pinonic acid. Gaschromatographic analyses of esters of the pinic acid gave two peakswhich presumably resulted from the expected cis and trans isomers of theacid.

EXAMPLE 2 Morpholine, 378 g. (4.35 moles) dissolved in l liter of drybenzene was heated to reflux. The acid chloride above was added dropwiseat a rate to maintain a gentle boil. When cooled to room temperature,morpholine hydrochloride, insoluble in benzene, was removed byfiltration and washed with benzene. After the solvent was removed underreduced pressure, the product was distilled. The yield was 444 g. of aliquid.

EXAMPLE 3 The amide above, 283 g. (1 mole), was dissolved in 300 ml. ofpercent ethanol and saponified by the addition of 40 g. of sodiumhydroxide dissolved in ml. of water. The temperature rose to 50 C. andafter 4 hours the pH dropped to about 8.. After 16 hours the batch wasdiluted with l69 ml. of water, the alcohol removed by distillation usinga packed column and the residue diluted further with 422 ml. of water.Extraction of the alkaline solution with chloroform gave 9.5 g. ofstarting material. Acidification, extraction with chloroform andisolation by removal of solvent at 0.5 mm., C. pot temperature gave 261g. of waxy solid. Five grams crude washed with diethyl ether gave 3 g.of colorless liquid, presumably the cis isomer since it was present inthe greater amount.

EXAMPLE 4 The crude half amide above was vinylated by the vinylinterchange procedure of Adelman (Adelman, R. L., J. Org. Chem., 14,1057 (1949)). The crude amide was melted and added in a molten state tothe vinyl acetate. After adding catalyst and standing awhile,crystallization of one of the half amide, presumably the cis isomeroccurred. After about 72 hours, the solid, about one-third of thecharge, was removed by filtration. The vinyl ester (filtrate)was'isolated by the usual procedure which involved stripping excessvinyl acetate in vacuo, washing with dilute sulfuric acid, 0.1 to 0.5 N,then water, drying over sodium sulfate and distilling. The recoveredacid was reacted with more vinyl acetate and converted to vinyl ester.

EXAMPLES The piperidine derivative was prepared as in example 2 exceptpiperidine was used in place of morpholine. The ethyl ester was thenhydrolyzed to the free acid as in example 3 and the monoamide wasvinylated by the vinyl interchange procedure as in example 4.

EXAMPLE 6 The di-n-butyl amine derivative was prepared as in example 2except di-n-butyl amine was'used in place of morpholine. The ethyl esterwas then hydrolyzed to the freeacid as in example 3 and the monoamidevinylated by the vinyl interchange procedure as in example 4.

EXAMPLE 7 The vinyl chioride copolymers containing 25 and 30 weightpercent of vinyl 2,2-dimethyl-3-morpholinocarbonylcyclobutane acetate,vinyl 2,2-dimethyl-3-piperidinocarbonylcyclobutane acetate and vinyl2,2-dimethyI-S-di-n-butylaminocarbonylcyclobutane acetate were preparedin the following manner:

Each evaluation sample was obtained by combining 10-15 individualpolymerization batches during the reprecipitation procedure. Eachindividual polymerization contained a starting charge of 10 g. ofmonomers (2.5 g. and 7.5 g. or 3.0 g. and 7.0 g. of the vinylester-amide and vinyl chloride, respectively). To a 1 10 ml.polymerization tube (Ace Glass T1506) was added the approximate amountof vinyl ester-amide, 0.6 g. of ORR soap, 4.0 ml. of a 2.5 percentpotassium persulfate solution and 43 ml. of deoxygenated water. Thevinyl 2,2- dimethyl-3-morpholinocarbonylcyclobutane acetate copolymerswere prepared using Triton X-301 (Rohm &

TABLE I.-VINYL ESTERS rubber.

The polymerization tubes were placed in a constant temperature tumblerbatch for 72 hours at 60 C. The copolymer emulsions were coagulated bypouring into 400 ml. of a saturated salt solution. The copolymer batchwas filtered, washed two times with water and two times with methanol.The copolymer was dissolved in tetrahydrofuran l0 percent solution) andreprecipitated a total 0t 15 times into water and 2 times into methanol.

A l-gallon Waring Blender was used for the reprecipitation into water.The rate of agitation was about 7,000 r.p.m. The methanol was stirredwith a spatula during the reprecipitations. The copolymers precipitatedin fibrous stands during the reprecipitation into water and methanolunder the conditions described.

The copolymers were dried in air for 72 hours and in a vacuum oven atroom temperature for 24 hours. The copolymer data are listed in table11.

OF AMIDES OF PINIO ACID Hydrogenation Composition, percent Vinyl2,2-dimethyl- Refracequivalent a-aminocarbonyltive Calculated Foundcyclobutane- M.P., 13.1 mm., Yield, index Calcuacctates C. C. Hg percento lated Found Formula C H N C H N Morpholinocar- 75 185 6. 2 81 1. 5018281. 34 280. 92 C15H2304N 6-1. 01 8. 24 4. 98 63. 03 8. 4. 85

carbonyl. Piperldinocarbonyl LiquitL 146-148 6. 18 53 1. 5007 279. 37280. 49 CreHzsOsN 68. 78 9. 02 5. 01 68. 90 J. 10 5. 06Di-n-butyl-amino- ..d0 150-152 0. 78. 2 1. 4765 325. 322. 16 ClflHiidOsN70. 53 10. 29 4. 33 70. 10. 18 4. 5]

carbonyl e Fron ether-pentane, 2:1.

TABLE II.EMULSION COPOLYME BIZATION OF VINYL CHLORIDE AND VINYLESTER-AMIDES AT 60 C. FOR 72 HOURS Weight Monomer Softening percentVinyl ester charge Convertemperaof (sample of each Water, S1011, ture.Anal." N lnher- I amide-ester Number) B batch b Emulsion, grams 1111.percent C. N percent ent f in copolymer Vinyl2,2-dimethyl-3-morpholinocarbonylcyclobutauo acetate:

25 riton X801 (3.0) 40 95 1. 83 0. 85 26. 5 43 82 91 1. 37 0. 27. 4 4078 9O 1. 11 0. 79 22. 2 43 76 1. 25 0. 96 19. 0

0 RR soap (0.5) 43 82 90 l. 20 1.15 23. 5 30 ORR soap (0.6) 45 79 001.14 1. 30 22. J di-n-butylaminocarbonylcyelobutane acetate: ORR soap(0.5)"... 43 75 80 1.18 1.28 26.4 25 .....do....- 43 84 1.09 1.34 23.730 d0 43 78 94 1.35 1.34 30.1

B Each polymer sample is a composite of 1015 individual polymerizationbatches. b Each polymerization bath contained 10 grams of monomer in theratio shown (weight percent of vinyl ester-amide) s Average conversion01' all batches after 2 reprecipitatio d The temperature at which thepolymer begins to flow 8 Average of two determinations.

ns into water. when heated between two cover glasses.

1 Inherent viscosity of a 0.2% tetrahydrofuran solution measured at 30C. in a No. 50 Cannon-Fenska viscometer. ll Calculated from the nitrogencontent of the copolymer.

TABLE IIL-PHYSICAL CHARACTERISTICS OF SOME POLY (VINYL ESTER-AMIDE-VINYL C11LO RIDE) COPOLYMERS Percent Relative estermodulus amideof elas- Yield Tensile Elon- Sample Vinyl ester-amide on N; ticity,point, strength, gatioii, Ti 3 T4. Number comonomer in polymer basisp.s.i. p.s.i. p.s.i. percent C- C.

1 26. 6 57. 400 2, 000 1,330 90 +10 +22 2 Vmyl z'g'dmethyla'mmphwna' 27.4 34, 200 1, 290 1, 230 +17 +24 3 carbonylcyclobutane acetate. 22. 2 62300 2' 470 1 630 15 5 +7 1 }Viny1 2,2-dirnethyl-3-piperidino- 25. 5 49,500 1, 800 1, 60 +10 +22 2 carbonylcyclobutane acetate. 22. 9 41, 300 1,604 1, 060 80 +7 +16 1 Vinyl 2,2-dirnethyl-3-din-butyl- 26. 4 30, 700 1,330 1, 200 100 +11 +21 2 aminocarbonylcyclobutane 23. 7 88, 400 4, 0303, 500 10 +14 +26 3 acetate. 30. 32, 900 1, 830 1,160 .10 +14 +22 Poly(vinyl chloride-vinyl acetate) None 7,700 6,830 128 +75 copolymer. Poly(vinyl chloride-vinyl acetate) do 1,600.... 3,050 850 24 3 copolymerplus 35% di-2-ethylhexyl phthalate.

h P.s.i. at 100% elongation. V W v Hass), a 20 percent solution of analkylaryl sulfonate and 40 70 We claim: ml. of water. The tube wascooled in a dry ice-acetone bath 1. A compound represented by theformula: and a slight excess of condensed vinyl chloride was added. The0 tube was capped with a crown-type bottle top after the excess n 1|vinyl chloride was evaporated. CH==CHO CCHZ The ORR soap mentioned aboveis a silicate free and linole- 75 A 9. CH3

ic acid linolinic acid free soap used in the production of GRS

